This invention relates to moisture curable ink compositions, particularly to those having reactive silyl functionality and their use.
Moisture-curable compositions cure in the presence of moisture to form crosslinked materials. The moisture is typically obtained from the atmosphere or from a substrate to which the composition has been applied, although it may be added to the composition.
Most moisture-curable compositions are based on isocyanate containing compounds. However, these compositions have well known disadvantages. Other moisture-curable compositions comprise polymers having groups (for example, alkoxysilyl or acyloxysilyl moieties) that react in the presence of moisture to form cured (i.e., crosslinked) materials. Moisture-curable compositions comprising alkoxysilyl or acyloxysilyl functionality typically cure in two reactions. In the first reaction, the alkoxysilyl or acyloxysilyl groups hydrolyze in the presence of moisture and a catalyst to form compounds having silanol groups. In the second reaction, the silanol groups condense with other silanol, alkoxysilyl, or acyloxysilyl groups in the presence of a catalyst to form xe2x80x94Sixe2x80x94Oxe2x80x94Sixe2x80x94 linkages. The two reactions occur essentially simultaneously upon generation of the silanol-functional compound. Commonly used catalysts for the two reactions include Brxc3x6nsted and Lewis acids. A single material may catalyze both reactions.
The hydrolysis reaction is schematically illustrated below for a polymer having alkoxysilyl groups: 
The resulting silanol (SiOH) groups are not stable in the presence of the acid catalyst and immediately condense with other silanol or alkoxysilyl group to form Oxe2x80x94Sixe2x80x94Oxe2x80x94Sixe2x80x94 linkages as shown below schematically for the condensation reaction of a silanol-functional compound and an alkoxysilyl-functional compound: 
Preferably, the hydrolysis and condensation reactions proceed quickly once the moisture-curable composition has been applied, for example, to a substrate.
Such compositions have been described as being useful as adhesives, sealants, and coatings.
Some known silane ink compositions contain an acid or a base added as catalysts in the ink binder. Such inks tend to have short pot-lives. The shelf life of such ink compositions is dependent upon the concentration of hydrolyzible silane compounds so the inks typically contain large amounts of solvents or water. Attempts to increase the shelf life of such inks include first hydrolyzing and condensing the alkoxysilyl compounds under controlled conditions and then use the reaction product as part of the ink binder.
Other curable siloxane ink compositions do not contain a catalyst, in some instances, to increase that storage stability of the ink. These inks require that they be heated to 150-200xc2x0 C. for 5-10 minutes to accelerate the hydrolysis reaction or that they are reacted very slowly at controlled temperature and humidity. Inks that require heating are not suitable for use on substrates that have a relatively low melting point or are easily distorted with heat. And, such slow curing will affect the printing resolution, due to uncontrolled spread of the drops, and color bleeding.
Most curable inks are based on acrylate and epoxy chemistries. The acrylate based inks cure rapidly by free-radical reaction and have good weatherability. However, the acrylate-based inks also typically suffer from oxygen inhibition during cure and surface shrinkage that can contribute to low gloss.
Epoxy-based inks have less shrinkage than acrylate-based inks, provide good adhesion, and have no oxygen inhibition during cure. However, epoxy-based inks typically provide poor weatherability and may have relatively slow cationic reaction rates as compared to free radical reaction rates.
The invention provides curable ink compositions that are inkjet printable and that adhere to a variety of substrates, for example, glass and polymer. xe2x80x9cCurablexe2x80x9d means that either reactive silyl groups hydrolyze in the presence of moisture to form compounds having silanol groups that react in the presence of an activated catalyst to form xe2x80x94Sixe2x80x94Oxe2x80x94Sixe2x80x94 linkages or silanol groups react in the presence of an activated catalyst to form xe2x80x94Sixe2x80x94Oxe2x80x94Sixe2x80x94 linkages.
The ink compositions of the invention can be formulated so as to provide cured inks that are very flexible, that is, polydimethylsiloxane, or very rigid, that is, silicate, depending upon the desired application. The curable ink compositions are also shelf stable and are cured-on-demand in that they may be cured rapidly at a predetermined time. xe2x80x9cShelf stablexe2x80x9d means that the compositions are stable in a light protected container for at least 3 weeks and preferably for at least 6 months. The ink compositions of the invention also provide inks having high gloss and transparency. The ink compositions of the invention also are not required to be diluted with water or solvent in order to be stable.
In one aspect, the invention provides a cure-on-demand curable ink composition comprising a homogeneous mixture of at least one of: (a) a compound having 2 reactive silyl groups, and (b) a compound having at least 3 reactive silyl groups; acid generating catalyst; and pigment or pigment chip. The acid generating catalyst may be activated (liberate a Brxc3x6nsted or Lewis acid) by heat or irradiating the composition with, for example, ultraviolet, visible light, electron beam, or microwave radiation.
In another aspect, the invention provides inks that are ink-jet printable.
In another aspect, the invention provides imaged ceramic articles comprising a cured ink composition of the invention on a ceramic substrate.
In another aspect, the invention provides a method of making a cure-on-demand curable ink composition comprising the steps of:
sequentially combining a compound having at least 3 reactive silyl groups, pigment chip, and acid generating catalyst with constant mixing.
In another aspect, the invention provides a method of forming an imaged article comprising the step of inkjet printing a moisture curable ink composition of the invention onto a substrate.
In another aspect, the invention provides a cure-on-demand curable composition for overprinting images comprising a homogeneous mixture of at least one of: (a) a compound having 2 reactive silyl groups, and (b) a compound having at least 3 reactive silyl groups; and acid generating catalyst.
The curable ink compositions of the invention can be formulated to have excellent adhesion to a variety of substrates, for example, those of polymethylmethacrylate (PMMA), silicone rubber, ceramics, and glass. The ink compositions of the invention also cure rapidly at room temperature and are expected to have excellent outdoor weatherability due to their inorganic backbone.
Reactive Silyl Functional Compounds
The curable ink compositions of the invention contain at least one of 1) a compound having at least two reactive silyl groups per molecule, typically a silicon atom bonded to either two hydroxysilyl groups or two alkoxysilyl groups and 2) a compound having at least 3 reactive silyl groups per molecule. The ink compositions of the invention also may contain a mixture of compounds from both of the above classes of compounds.
Reactive silyl functional compounds useful in the invention can incorporate a wide variety of backbones to support the reactive silyl groups and, as a result, such compounds may be generally represented by the following structures: 
wherein,
A is a k-valent group which may be selected from, for example, a chemical bond (i.e., no atoms); xe2x80x94OR; alkyl groups (preferably having 1 to 30, more preferably, 12 to 20 carbon atoms); cycloalkyl groups (preferably having 3 to 30, more preferably, 6 to 10 carbon atoms), aryl groups (preferably having from 6 to about 30 carbon atoms); a chalcogen (group VIb elements), such as oxygen, sulfur, etc., and polymeric radicals which may be of linear, branched, block, or graft construction. Non-limiting examples of suitable polymeric groups include polysiloxanes, polyacrylates, polyamides, polyolefins, polyethers, polyesters, polyurethanes and polyphosphazenes, as well as derivatives and combinations thereof. The polymeric groups may be hydroxy-(to form a silanol), acyloxy-, or alkoxy-terminated or may have pendent silanol, acyloxysilyl, or alkoxysilyl groups.
Each G independently represents an optional multi-valent group having a valence of at least 2. Non-limiting examples of G include xe2x80x94Si(OR)xe2x80x94 wherein x=0-2, hydrocarbon diyls and oxydiyls, particularly alkanediyls and oxydiyls, such as methylidene, ethylidene, 1,3-propanediyl, 1,5-pentanediyl, 2-oxo-propanediyl, phenylene (an arenediyl); chalcogens, such as oxygen, sulfur, etc.; hydrocarbon triyls, such as, for example, pentaerythritoltriyl; and the like. The exact nature of G is not critical so long as it does not contain groups that inhibit the condensation cure of alkoxy- or hydroxysilyl groups.
Each R1 independently represents hydrogen, an alkyl group (preferably having 1 to 30, more preferably, 1 to 4 carbon atoms), a cycloalkyl group (preferably having 3 to 30, more preferably, 6 to 10 carbon atoms), an alkanoyl group (preferably having 2 to 30, more preferably, 2 to 4 carbon atoms), or an aroyl group (preferably having from 7 to about 30 carbon atoms).
Each R independently represents hydrogen, an alkyl group (preferably having 1 to 30, more preferably, 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30, more preferably, 6 to 10 carbon atoms), an alkanoyl group (preferably having 2 to 30, more preferably, 2 to 10 carbon atoms), or an aroyl group (preferably having from 7 to about 30 carbon atoms).
Each n is either 0, 1, or 2 with the proviso that compounds from either Structure 1 or Structure 2 above have at least two reactive silyl groups; each j independently represents 0 or an integer greater than or equal to 1; k represents an integer greater than or equal to 1; and m represents an integer greater than or equal to 3.
As is well understood in this area, substitution is not only tolerated, but also is often advisable and substitution is anticipated on the compounds used in the present invention. As a means of simplifying the discussion and recitation of certain substituent groups, the terms xe2x80x9cgroupxe2x80x9d and xe2x80x9cmoietyxe2x80x9d are used to differentiate between those chemical species that may be substituted and those which may not be so substituted. Thus, when the term xe2x80x9cgroupxe2x80x9d or xe2x80x9caryl groupxe2x80x9d is used to describe a substituent, that substituent includes the use of additional substituents beyond the literal definition of the basic group. Where the term xe2x80x9cmoietyxe2x80x9d is used to describe a substituent, only the unsubstituted group is intended to be included. For example, the phrase, xe2x80x9calkyl groupxe2x80x9d is intended to include not only pure hydrocarbon alkyl chains, such as methyl, ethyl, propyl, t-butyl, cyclohexyl, iso-octyl, octadecyl and the like, but also alkyl chains bearing substituents known in the art, such as hydroxyl, alkoxy, phenyl, halogen atoms (F, Cl, Br, and I), cyano, nitro, carboxy, etc. For example, alkyl group includes ether groups (e.g., CH2 CH2CH2xe2x80x94Oxe2x80x94), haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc.
On the other hand, the phrase xe2x80x9calkyl moietyxe2x80x9d is limited to the inclusion of only pure hydrocarbon alkyl chains, such as methyl, ethyl, propyl, t-butyl, iso-octyl, octadecyl, and the like. Substituents that react with active ingredients, such as very strongly electrophilic or oxidizing substituents, or basic materials that would substantially interfere with the cationic curing catalyst (e.g., tertiary amines, etc.) would of course be excluded by the ordinarily skilled artisan as not being inert or harmless.
As noted above, preferred groups for radical A include silanol- or alkoxy-terminated polysiloxanes, polyacrylates, polyolefins and polyethers.
1. Difunctional Silane Compounds
The compositions of the invention can contain at least one difunctional silane compound, for example, having either two silanol groups or two alkoxysilyl groups per molecule. These compounds provide a polymer backbone and adjust crosslink density of the cured inks.
Nonlimiting, specific examples of compounds described above include hydroxy and/or alkoxy terminated polydimethylsiloxanes having a molecular weight of 400 to 150,000; hydroxy and/or alkoxy terminated diphenylsiloxane-dimethylsiloxane copolymers; hydroxy and/or alkoxy terminated polydiphenylsiloxanes; hydroxysilyl and/or alkoxysilyl terminated polytrifluoropropylmethylsiloxanes, polyesters, polyurethanes, and polyacrylates; dialkyl- and substituted dialkyl- dialkoxysilanes, such as diethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisobutyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, bis(3-cyanopropyl)dimethoxysilane, (2-chloroethyl)methyldimethoxysilane, chloromethylmethyldiethoxysilane, (2-chloroethyl)methyldiisopropoxysilane, (3-chloropropyl)methyldimethoxysilane,(3-cyanopropyl)methyldimethoxysilane, cyclohexylethyldimethoxysilane, dodecylmethyldiethoxysilane, isobutylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane; mercaptomethylmethyldiethsysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methyldiethoxysilane, methyldimethoxysilane, n-octadecylmethyldiethoxysilane; n-octylmethyldiethoxysilane, dicyclopentyldimethoxysilane, etc.; aryl and diaryl substituted alkoxysilanes, such as diphenyldimethoxysilane, phenyldiethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, etc.; hydroxysilyl and alkoxysilyl substituted arenes, such as 1,4-bis(hydroxydimethylsilyl)benzene, 1,3-bis(methoxydimethylsilyl)benzene, etc.; trialkylsilyl substituted alkoxysilanes, such as bis(trimethylsilylmethyl)dimethoxysilane, trimethylsilylmethyldimethoxysilane,etc.; cyclic alkoxysilanes, such as 1,1-diethoxy-1-silacyclopent-3-ene, etc.; acyloxy substituted silanes, such as dimethyldiacetoxysilane, vinylmethyldiacetoxysilane, diethylbenzoyloxyacetoxysilane, etc; geminal silanediols, such as diphenylsilanediol, dicyclohexylsilanediol, etc.; alkyl and/or aryl substituted cyclic siloxanes, such as 3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane, hexamethyltrisiloxane, octamethyltetrasiloxane, etc.; alkenyl substituted alkoxysilanes, such as vinylethyldiethoxysilane, vinylmethyldimethoxysilane, vinylphenyldiethoxysilane, and the like.
Presently preferred compounds having 2 reactive silyl groups are hydroxy terminated polydimethylsiloxanes and polydiethylsiloxanes (i.e., having Sixe2x80x94OH terminal groups).
2. Silanes Having at Least 3 Reactive Silyl Groups
The compositions of the invention can contain at least one compound having at least 3 and preferably, from 4 to 6 reactive silyl groups per molecule. The reactive silyl groups can be, for example, alkoxy silyl or acyloxy silyl groups.
Nonlimiting, specific examples of compounds described above include trifunctional crosslinkers, such as, for example, isobutyltrimethoxysilane, methytriethoxysilane, methytrimethoxysilane, octyltriethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, chloropropyltriethoxysilane, chloropropyltriethoxysilane, mercaptopropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane; tetrafunctional crosslinkers, such as, for example, tetramethoxysilane, tetraethoxysilane, 1,3-dimethyltetramethoxydisiloxane, 1,3-di-n-octyltetramethoxydisiloxane, 1,3-divinyltetraethoxydisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, tetrakis(butoxyethoxyethoxy)silane, tetrakis(ethoxyethoxy)silane, tetrakis(trimethylsiloxy)silane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-methacryloxyethoxysilane), tetrakis(methoxyethoxyethoxy)silane, tetrakis(methoxyethoxy)silane, tetrakis(methoxypropoxy)silane, tetra-n-propoxysilane; higher functionality crosslinkers, such as bis[3-(methyldimethoxysilyl)propyl]polypropylene oxide, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bio(triethoxysilyl)methane, 1,9-bis(triethoxysilyl)nonane, bis(triethoxysilyl)1,7-octadiene, bis(triethoxysilyl)octane, bis[3-(triethoxysilyl)propyl]-tetrasulfide, bis(3-(triethoxysilyl)propyl)urea, bis(trimethoxysilyl)ethane, 1,4-bis(trimethoxysilylethyl)benzene, bis(trimethoxysilyl)hexane, bis(trimethylsiloxy)cyclobutene, di-t-butoxydiacetoxysilane, hexamethoxydisilane, hexaethoxydisilane, tetraacetoxysilane, tetraallyloxysilane, tetra-n-butoxysilane, 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, and functional polymers, such as poly(diethoxysiloxane), diethoxysiloxane-s-butylaluminate copolymers, diethoxysiloxane-ethyltitanate copolymers, diethoxysiloxane-ethyl phosphate copolymers, and the like.
Presently preferred compounds having 3 or more reactive silane groups are 1,3-dimethyltetramethoxydisiloxane, methacryloxypropyltrimethoxysilane, tetraethoxysilane, 1,3-dioctyltetramethoxydisiloxane, glycidoxypropyltrimethoxysilane, 3-bromopropyltrimethoxysilane, and dioctyltetraethoxydisiloxane.
Preferably, the reactive silyl functional groups are the only acid curable groups in the ink composition.
Acid Generating Catalysts
Upon activation, the acid generating catalyst liberates an acid that initiates and/or accelerates curing (i.e., crosslinking) of the curable ink composition. In order to facilitate more rapid curing, the liberated acid preferably has a pKa of less than about 3, more preferably less than about 1. Activation may be accomplished by heat or irradiating the composition with, for example, ultraviolet, visible light, electron beam or microwave radiation. Moisture required for the initial hydrolysis reaction of the curing mechanism may be obtained from, for example, the substrate, the composition itself, or, most commonly, atmospheric humidity. The catalyst is typically present in an amount of about 0.5 to about 20 parts by weight, preferably from about 1 to about 10 parts by weight, more preferably from about 2 to about 7 parts by weight based on 100 parts by weight reactive silane functional compounds.
A variety of catalysts may be used in the practice of the invention except for those containing basic species, such as ammonium salts disclosed in U.S. Pat. No. 5,286,815 that generate an amine that may inhibit the curing reaction of the cure-on-demand composition of this invention. Thus, catalysts of the present invention are substantially free of ammonium salts. Minor amounts of such salts may be tolerated without greatly affecting the care rate. Particularly desired catalysts for use in this invention are those that are capable of releasing an acid upon exposure to ultraviolet or visible light or upon exposure to electron beam irradiation. Preferably, the catalyst comprises an onium salt because of their capacity to simultaneously generate a strong acid and an energetic free radical when activated.
Onium salts suitable for use in the present invention are preferably sulfonium or iodonium salts having the following structure:
LWxe2x80x94Y+MXxe2x88x92xe2x80x83xe2x80x83Structure 3
L is an aryl or substituted aryl group; w is an integer from 2 to 4; Y is sulfur or iodine; M is a Group III, IV, or V element from the Periodic Table of the Elements; and X is a sulfate, tosylate, alkylsulfonate, fluoroalkylsulfonate, fluoroalkyl, or a perfluorinated aryl group.
Examples of useful sulfonium salts include:
triphenylsulfonium tetrafluoroborate;
triphenylsulfonium tetrakis(pentafluorobenzyl)borate;
methyldiphenylsulfonium tetrafluoroborate;
methyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate;
dimethylphenylsulfonium hexafluorophosphate;
triphenylsulfonium hexafluorophosphate;
triphenylsulfonium hexafluoroantimonate;
diphenylnaphthylsulfonium hexafluoroarsenate;
tritolysulfonium hexafluorophosphate;
anisyldiphenylsulfonium hexafluorantimonate;
4-butoxyphenyldiphenylsulfonium tetrafluoroborate;
4-butoxyphenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate;
4-chlorophenyldiphenylsulfonium hexafluoroantimonate;
tris(4-phenoxyphenyl)sulfonium hexafluorophosphate;
di(4-ethoxyphenyl)methylsulfonium hexafluoroarsenate;
4-acetylphenyldiphenylsulfonium tetrafluoroborate;
4-acetylphenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate;
tris(4-thiomethoxyphenyl)sulfonium hexafluorophosphate;
di(methoxysulfonylphenyl)methylsulfonium hexafluoroantimonate;
di(methoxynaphthyl)methylsulfonium tetrafluoroborate;
di(methoxynaphthyl)methylsulfonium tetrakis(pentafluorobenzyl)borate;
di(carbomethoxyphenyl)methylsulfonium hexafluorophosphate;
(4-octyloxyphenyl)diphenylsulfonium tetrakis(3,5-bis-trifluoromethyl-phenyl)borate;
tris(dodecylphenyl)sulfonium tetrakis(3,5-bis-trifluoromethylphenyl)borate;
4-acetamidophenyldiphenylsulfonium tetrafluoroborate;
4-acetamidophenyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate;
dimethylnaphthylsulfonium hexafluorophosphate;
trifluoromethyldiphenylsulfonium tetrafluoroborate;
trifluoromethyldiphenylsulfonium tetrakis(pentafluorobenzyl)borate;
phenylmethylbenzylsulfonium hexafluorophosphate;
10-methylphenoxathiinium hexafluorophosphate;
5-methylthianthrenium hexafluorophosphate;
10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate;
10-phenyl-9-oxothioxanthenium tetrafluoroborate;
10-phenyl-9-oxothioxanthenium tetrakis(pentafluorobenzyl)borate;
5-methyl-10-oxothianthrenium tetrafluoroborate;
5-methyl-10-oxothianthrenium tetrakis(pentafluorobenzyl)borate; and
5-methyl-10,10-dioxothianthrenium hexafluorophosphate.
Examples of useful iodonium salts include: di(dodecylphenyl)iodonium hexafluoroantimonate, di(dodecylphenyl)iodonium triflate; diphenyliodonium bisulfate, 4,4xe2x80x2-dichlorodiphenyliodonium bisulfate; 4,4xe2x80x2-dibromodiphenyliodonium bisulfate; 3,3xe2x80x2-dinitrodiphenyliodonium bisulfate; 4,4xe2x80x2-dimethyldiphenyliodonium bisulfate; 4,4xe2x80x2-bissuccinimidodiphenyliodonium bisulfate; 3-nitrodiphenyliodonium bisulfate; 4,4xe2x80x2-dimethoxydiphenyliodonium bisulfate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate; (4-octyloxyphenyl)phenyliodonium tetrakis(3,5-bis-trifluoromethyl phenyl)borate; (tolylcumyl)iodonium tetrakis(pentafluorophenyl)borate (CH3C6H4)2Ixe2x80x94(SO2CF3)3, as disclosed in U.S. Pat. No. 5,554,664; (C6H5)2Ixe2x80x94B(C6F5)4, as disclosed in U.S. Pat. No. 5,514,728; and those disclosed in U.S. Pat. No. 5,340,898. A particularly preferred onium salt is di(dodecylphenyl)iodonium hexafluoroantimonate.
Onium salts are typically activated using ultraviolet radiation. Because of this, they can be advantageously employed in applications involving heat-sensitive substrates. Optionally, a sensitizer may supplement the onium salt to accelerate the liberation of the acid catalyst and typical amounts are about 0.03 to about 0.1 parts by weight, based on 100 parts by weight reactive silane functional compound. Examples of suitable sensitizers include those described in Chapter 13 of Radiation Curing in Polymer Science and Technology, Vol. 2, edited by Fouassier and Rabek, Elsevier Science Publishers LTD, 1993. 2-isopropylthioxanthone is a particularly preferred sensitizer for use with di(dodecylphenyl)iodonium hexafluoroantimonate.
Pigments
The ink compositions of the invention contain one or more pigments. Suitable organic and inorganic pigments include carbon black, zinc oxide, titanium dioxide, phthalocyanine, anthraquinones, perylenes, carbazoles, monoazo- and disazobenzimidazolones, rhodamines, indigoids, quinacridones, diazopyranthrones, dinitranilines, pyrazolones, diazopyranthrones, dinitranilines, pyrazolones, dianisidines, pyranthrones, tetracholoroisoindolinones, dioxazines, monoazoacrylides, and anthrapyrimidines. It will be recognized by those skilled in the art that organic pigments will be differently shaded, or even have different colors, depending on the functional groups attached to the main molecule.
Commercial examples of useful organic pigments include those known under the C.I. (i.e., Colour Index International, 3rd ed., 4th revision (1992-); The Society of Dyers and Colourists, Bradford, West Yorkshire, England) trade designations PB 1, PB 15, PB15:1, PB15:2, PB15:3, PB15:4, PB15:5, PB15:6, PB16, and PB 60 (blue pigment); PB5, PB23, and PB 265 (brown pigment); PG1, PG7, PG 10, PG 36 (green pigment); PY 3, PY 14, PY 16, PY 17, PY 24, PY 65, PY73, PY 83, PY 95, PY 97, PY 108, PY 109, PY 110, PY 113, PY 128, PY 129, PY 138, PY 139, PY 150, PY 154, PY 156, and PY 175 (yellow pigment); PO 5, PO15, PO 16, PO31, PO34, PO 36, PO43, PO48, PO 51, PO 60 and PO 61 (orange pigments); PR4, PR5, PR 7, PR 9, PR222, PR23, PR48, PR48:2, PR 49, PR112, PR123, PR 149, PR166, PR 168, PR 170, PR 177, PR 179, PR 190, PR 202, PR 206, PR 207, PR 224 (red); PV 19, PV 23, PV 37, PV 32 and PV 42 (violet pigments); and PBLACK (black).
The pigments are milled so to incorporate into selected curable ink vehicles. If used as inkjet inks, the pigment preferably is less than 1 micrometer in size after milling. If the ink to be used in application wherein the ink is used in combination with a retroreflective backing, the pigment must be milled to a particle size that provide sufficient transparency to permit retroreflection and provide retroreflective color. The preferred range for the pigment particle size is about 10-400 nm, more preferably 10 to 200 nm, to provide the desired transparency.
In some cases, pigment is ground with a non-reactive binder resin which separates pigment particles and prevents them from coalescing. Such solid/solid dispersion, referred to as pigment chip, maintains pigment particle size until the pigment is ready to be incorporated into the ink. The ratio of pigment to binder resin in the supplied chip is usually about 1:1 to 9:1. Useful binder resins for use in the inks of the current invention are well known in the pigment dispersion art and include cellulosic resins, such as ethyl cellulose, cellulose acetate, nitrocellulose, etc.; acrylic resins, such as those sold under the trade designation JONCRYL from S. C. Johnson Wax, Racine, Wis; polyacetal resins, such as polyvinyl butral (for example, those sold under the trade designation BUTVAR from Monsanto Co., St. Louis, Mo.) and polyvinyl formal (for example, those sold under the trade designation FORMVAR from Monsanto Co.); and modified rosin ester resins and the like.
The preferred pigment chip in the ink of the current invention contains pigments, such as titanium dioxide or carbon black and ethyl cellulose resin. Such pigment chips are available under the trade name MICROLITH White R-A and MICROLITH Black C-A from Ciba Specialty Chemicals Division, Newport, Del.
An effective amount of pigment is used to provide the desired color and intensity to the ink. The vehicle maybe be used, for example, in an amount ranging from about 20-99.9 percent of the weight of the total composition and a colorant from about 0.1 to 80 percent of the total composition.
Solvents
A solvent may be included in the ink compositions of the invention to decrease the viscosity of the composition. Solvent should be miscible with the other components of the ink compositions of the invention. Examples of useful solvents include ketones and alcohols. Suitable ketones include acetone, cyclohexanone, and methyl ethyl ketone. Suitable alcohols include methanol and ethanol. Other solvents that may be useful include acetonitrile, carbon tetrachloride, dichloroethane, dicloromethane, dimethylformamide, dimethylsulfoxide, ethyl acetate, diethyl ether, diisopropyl ether, tetrachloroethane, tetrahydrofuran, and trichloroethane. If present, solvent may be from 0.1 to 30 percent, preferably, 0.1 to 10 percent by weight of the ink composition, more preferably, less than 10 percent and even more preferably, solvent free.
Optional Additives
Conventional additives, such as flow agents, leveling agents, viscosity modifiers, antioxidants, hindered amine light stabilizers, UV light absorbers, electrolytes (to provide electrical conductivity), and the like, may be added to the compositions of the invention. If used, these additives may be individually present in an amount ranging from about 0.5 to 5 weight percent of the ink composition.
Ink Compositions
Preparation of stable curable ink compositions of the invention is readily accomplished through the following procedures. Preparation of stable inks of the invention is not readily achieved by simply mixing pigment into the ink vehicle.
However, it has been found that if pigment chip is being used, a dispersibility test is run to determine the ability of the at least trifunctional silane to disperse the pigment chip. The dispersibility test is as follows: 0.1 g of the pigment chip to be dispersed in the ink and having the desired particle size is added to a clear glass vial containing 1.0 g of at least trifunctional silane. The ink in the container is vigorously stirred with a stirring rod for 1 minute and then allowed to stand for about 10 minutes. If no settling of the pigment is observed when viewing through the vial, then the test is passed and is considered to be dispersible.
In the event that the pigment chip dispersibility test is passed, then the ink composition may be prepared by sequentially combining, in a container equipped with mixing means, at least trifunctional silane, pigment chip, difunctional silane, curative, and any optional solvent (to be used reduce viscosity).
In the event that the pigment chip dispersibility test is failed, then the ink composition may be prepared in a container equipped with mixing means, by sequentially combining (in order) pigment chip, sufficient solvent to create a homogeneous solution, at least a trifunctional silane, difunctional silane, curative, and any optional solvent.
In the event that regular pigment is used to make the curable ink compositions of the invention, then the ink composition may be prepared by sequentially combining, in a container equipped with mixing means, a silicone surfactant, pigment, any optional at least trifunctional silane, difunctional silane and processing for sufficient time so as to form a dispersion concentrate. Then curative and any optional solvent is added with mixing.
Useful silicone surfactants include polyalkylene oxide modified polydimethylsiloxane (mw=100-15,000 g/mol, preferably, 300-5000 g/mol). Examples include SILWET L77, L7608, L7280, L7607, L722, L7500, L7602, L7622, L7604, L7057, L7605, L7600, and L7002 and are available from Witco Corp., Greenwich, Conn.
In the event that a phthalocyanine pigment is used to make the curable ink compositions of the invention, then the ink composition may optionally also be prepared by sequentially combining, in a container equipped with mixing means, pigment, any optional at least trifunctional silane, difunctional silane, and processing for sufficient time so as to form a dispersion concentrate. Curative, and any optional solvent is added with mixing. xe2x80x9cMixing meansxe2x80x9d includes shearing mixers, two or three roll mills, media mills, ball mills, agitators, and the like.
The physical properties and adhesion characteristics of the inks of the invention may be tailored for specific end uses. The characteristics of the cured inks largely depend upon the ratio of difunctional silanes and at least trifunctional silanes. For example, inks that are generally pliable and have good adhesion to low surface energy substrates usually contain more difunctional silane than at least trifunctional silane. On the other hand, inks that are generally rigid and which have good adhesion to surface, such as glass and ceramic usually contain more at least trifunctional silane than difunctional silane.
The ink compositions which are generally pliable after cure contain from about 10 to about 90 weight percent compound having 2 reactive silyl groups, from about 5 to about 40 weight percent compound having at least 3 reactive silyl groups, from about 0.1 to about 20 percent by weight acid generating catalyst, and from about 0.1 to about 80 percent by weight pigment. The preferred ranges are about 30 to about 50 weight percent compound having 2 reactive silyl groups, from about 15 to about 25 weight percent of compound having at least 3 reactive silyl groups, from about 0.5 to about 5 weight percent acid generating catalyst, and from about 2 to about 15 weight percent pigment.
The ink compositions which are generally rigid after cure and have good adhesion to glass and ceramic contain from 0 to about 10 weight percent of compound having 2 reactive silyl groups, from about 40 to about 95 weight percent of compound having at least 3 reactive silyl groups, from about 0.1 to about 20 weight percent acid generating catalyst, and from about 0.2 to about 80 weight percent pigment. The preferred ranges are from about 2 to about 5 weight percent of compound having 2 reactive silyl groups, from about 50 to about 80 weight percent of compound having at least three reactive silyl groups, from about 0.5 to about 5 weight percent of acid generating catalyst, and from about 2 to about 15 weight percent pigment.
The ink compositions of the invention can have a Brookfield viscosity of up to about 50 cps (mPa s) preferably about 25 cps (mPa s), more preferably less than about 15 cps (mPa s) at 25xc2x0 C.
The ink compositions of the invention may be applied to a substrate using conventional ink printing techniques, such as screen printing, flexographic, and offset, etc. However, the ink compositions of the invention are particularly well adapted for ink-jet printing techniques. Once printed, the ink compositions will react with the moisture in the ambient air and/or the catalyst will be activated by UV light and form cured ink. The cured ink may be rigid or pliable depending upon the specific formula of ingredients used.
In some instances, it may be desirable to further heat the substrate and the ink until the ink is converted into a ceramic material free of carbonaceous matter, that is, to pyrolyze the printed substrate.
Once a substrate has been imaged with ink of the invention, it may be desirable to coat the image with a pigment-free or clear coat composition to enhance weatherability and durability of the image. Such clear coat compositions can be made by combining acid generating catalyst with at least one of: (a) a compound having 2 reactive silyl groups, and (b) a compound having at least 3 reactive silyl groups. The characteristics of the clear coat compositions can be tailored as described above for the ink compositions. The clear coat compositions may be applied over the image using any means and is preferably applied over the image and/or substrate using inkjet printing techniques.